CN113122895B - Method for regulating and controlling electrochemical induced mineral deposition rate by parallel connection of cathodes - Google Patents
Method for regulating and controlling electrochemical induced mineral deposition rate by parallel connection of cathodes Download PDFInfo
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- CN113122895B CN113122895B CN202110295995.9A CN202110295995A CN113122895B CN 113122895 B CN113122895 B CN 113122895B CN 202110295995 A CN202110295995 A CN 202110295995A CN 113122895 B CN113122895 B CN 113122895B
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- C25D9/00—Electrolytic coating other than with metals
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Abstract
The invention relates to a method for regulating and controlling the deposition rate of electrochemically induced minerals by connecting cathodes in parallel, which comprises the following steps: (1) constructing an electrode system consisting of cathodes, anodes and electrolyte solution, wherein the number of the cathodes is two, and the anodes are respectively fixed on the outer sides of the two cathodes; (2) and adjusting the distance between the two cathodes to realize the regulation and control of the mineral deposition rate on the surface of the cathode. Compared with the prior art, the invention realizes the effective regulation and control of the mineral growth rate on the premise of keeping the cathode current density and the properties of the inorganic minerals unchanged, and lays a solid foundation for the application of the technology in the field of building materials.
Description
Technical Field
The invention belongs to the technical field of electrochemical deposition, and relates to a method for regulating and controlling the deposition rate of electrochemically-induced minerals by parallel connection of cathodes.
Background
Electrochemical deposition technology has been widely applied in the fields of metal, nanometer and thin film, and the conductivity of the deposit is closely related to the continuity and uniformity of the deposit. Therefore, the development of this technology in the field of non-conductive inorganic minerals is not advantageous. At present, the technology of electrodepositing inorganic minerals is mainly applied to the fields of concrete crack repair, cathodic protection and the like. Hilbertz first proposed a technique for preparing an inorganic mineral building material in situ in seawater using an electrochemical deposition technique in the last 70 th century. In recent years, scholars explore the influence rule of parameters such as current density and cathode materials on the growth of the electrodeposit; the main component of the deposit is determined to be Mg (OH) 2 And a small amount of CaCO 3 (ii) a Meanwhile, the mechanical properties of the sediment are researched, and the potential of the inorganic mineral applied to the field of buildings is established. However, the low growth rate of the mineral is the biggest problem in the development of the technology. At present, the main means for increasing the growth rate of the deposit is to increase the current density on the cathode surface, and the method is only effective in a certain current density range, and because the cathode surface H 2 The bubble generation rate also increases with increasing current density, and bubbles have a large effect on the mechanical properties of the deposit, even leading to flaking of the deposit from the cathode surface. Therefore, on the premise of not influencing the self properties of inorganic minerals on the surface of the cathode, the improvement of the growth rate of the sediments is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling the deposition rate of an electrochemically induced mineral in parallel by a cathode, which effectively improves the in-situ growth rate of an electro-deposit on the basis of not influencing the property of the deposited mineral, thereby laying a solid foundation for the application of the electrochemically induced mineral in the field of buildings.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for regulating and controlling the deposition rate of electrochemically induced minerals by connecting cathodes in parallel, which comprises the following steps:
(1) constructing an electrode system consisting of cathodes, anodes and electrolyte solution, wherein the number of the cathodes is two, and the anodes are respectively fixed on the outer sides of the two cathodes;
(2) and adjusting the distance between the two cathodes to realize the regulation and control of the mineral deposition rate on the surface of the cathode.
Further, in the regulation and control process, the smaller the distance between the two cathodes is, the larger the mineral deposition rate on the surface of the cathode is increased.
Further, the two cathodes are respectively parallel to the anodes located at the outer sides thereof.
Further, the two cathodes are respectively at the same distance from the anode located at the outer side thereof.
Furthermore, the two cathodes are connected in parallel, and the materials and the sizes of the two cathodes are the same.
Further, the distance between the two cathodes is within 6 times of the width or diameter of the cathode, specifically, when the cathode is in a sheet shape or a net shape, the width is taken as a measuring standard, and when the cathode is in a rod shape or a column shape, the diameter is taken as a measuring standard.
Further, the cathode is a metal sheet, a metal mesh or a metal rod.
Further, the anode is a ruthenium iridium titanium sheet or a platinum sheet.
Further, the electrolyte solution is an aqueous solution containing magnesium ions and/or calcium ions.
Further, the cathode and the anode are respectively connected with the negative electrode and the positive electrode of an external power supply.
Compared with the existing regulation and control method, the method for improving the electrochemical induced mineral deposition rate by parallel connection of the cathodes has the following innovation points and advantages: the cathode is connected in parallel to realize the OH on the surface of the cathode - Concentration superposition realizes the OH on the surface of the cathode on the premise of not changing the current density - The concentration is increased, and then Mg (OH) is increased 2 The formation rate of the insoluble minerals on the cathode surface. The mode avoids the adverse effect of current density increase on the pore structure of the sediment, effectively shortens the period of electrochemically inducing mineral deposition, improves the deposition efficiency and reduces the production energy consumption.
Drawings
FIG. 1 is a schematic diagram of a parallel connection of cathodes in accordance with the present invention;
the notation in the figure is:
1-external power supply, 2-lead, 3-anode I, 4-anode II, 5-cathode I and 6-cathode II.
FIG. 2 shows the parallel cathode surface OH - Concentration distribution and superposition.
Figure 3 is a photograph of parallel mesh cathodes and their resulting deposits.
FIG. 4 is a photograph of parallel rod cathodes spaced 0.5cm apart and the resulting deposits.
FIG. 5 is a photograph of parallel rod cathodes spaced 3.5cm apart and the resulting deposits.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In order to effectively improve the in-situ growth rate of the electrodeposit on the basis of not influencing the properties of the sedimentary minerals, thereby laying a solid foundation for the application of the electrochemically induced minerals in the field of construction, the invention provides a method for regulating the deposition rate of the electrochemically induced minerals in parallel by a cathode, which comprises the following steps as shown in figure 1:
(1) constructing an electrode system consisting of cathodes, anodes and electrolyte solution, wherein the number of the cathodes is two, and the anodes are respectively fixed on the outer sides of the two cathodes;
(2) and adjusting the distance between the two cathodes to realize the regulation and control of the mineral deposition rate on the surface of the cathode.
In some embodiments, the smaller the distance between two cathodes, the greater the increase in mineral deposition rate on the cathode surface during conditioning.
In some embodiments, the two cathodes are each parallel to the anode on the outside thereof.
In some embodiments, the two cathodes are each at the same distance from the anode located outside thereof.
In some embodiments, the two cathodes are connected in parallel, and the two cathodes are the same in material and size.
In some embodiments, the distance between the two cathodes is within 6 times the width or diameter of the cathode, specifically, the width of the cathode is used as a measuring reference when the cathode is in a sheet shape or a net shape, and the diameter of the cathode is used as a measuring reference when the cathode is in a rod shape or a column shape.
In some embodiments, the cathode is a metal sheet, a metal mesh, or a metal rod.
In some embodiments, the anode is a ruthenium iridium titanium plate or a platinum gold plate.
In some embodiments, the electrolyte solution is an aqueous solution comprising magnesium ions and/or calcium ions.
In some embodiments, the cathode and anode are connected to a negative electrode and a positive electrode, respectively, of an external power source.
In the invention, two cathodes made of the same material and with the same size are respectively connected with the negative electrode of an external power supply, namely the cathodes are connected in parallel. During the electrodeposition process, the reduction of water molecules to generate hydrogen (H) occurs on both cathode surfaces 2 ) And hydroxide ion (OH) - ) The reaction of (1). OH formed on the surface of the cathode - Diffusion takes place away from the cathode surface, i.e. OH in the solution near the cathode surface - Exists in a certain concentration gradient. And OH in solution between the two cathodes - The concentrations must be superposed with each other, and the superposed OH - Increased concentration of Mg near the cathode 2+ The probability of collision and combination of plasma metal ions is increased, and the result is Mg (OH) 2 And the growth rate of the insoluble crystal is improved. Notably, the cathode is connected in parallel to the lift depositAt the same time of growth rate, the current density on the surface of single cathode is not changed, namely the surface H of single cathode 2 The bubble generation rate is not increased, and the stability of the self property of the cathode deposit is realized.
The above embodiments may be implemented individually, or in any combination of two or more.
The above embodiments will be described in more detail with reference to specific examples.
A method for regulating and controlling the deposition rate of electrochemically induced minerals by connecting cathodes and anodes in parallel is disclosed, the connection mode of the cathodes and the anodes is shown in figure 1, the whole electrode system comprises an external power supply (which can be a direct current power supply) for providing current and a lead for transmitting the current, a first cathode and a second cathode which are made of the same material and have the same size and are mutually parallel and parallel, a first anode and a second anode which are respectively positioned at the outer sides of the first cathode and the second cathode, and OH on the surface of the cathode - The ion concentration distribution is schematically shown in fig. 2, and the two are overlapped.
The experiment of regulating the deposition rate of the electrochemically induced minerals in parallel with the cathodes was carried out in the manner described above, and the specific example is as follows.
Example 1:
selecting MgCl with the concentration of 0.15mol/L 2 0.03mol/L of CaCl 2 And 0.0069mol/L NaHCO 3 The mixed solution is used as an electrolyte solution; the anode material is a ruthenium iridium titanium rod with the diameter of 0.3cm, two pieces of 304 stainless steel nets (the wire diameter is 0.5mm and the pore diameter is 3.8mm) with the diameter of 6cm to 5cm are selected as the cathode, the distance between the cathode and the anode is controlled to be 4cm, the distance between the cathodes connected in parallel is controlled to be 1cm, and the depth of the liquid level of the electrode immersed is controlled to be 6 cm; the external power supply selects a voltage-stabilizing direct-current power supply, a constant current mode is adopted, and the current is set to be 20 mA; the electrolyte solution is replaced every 24 hours to ensure that the electrolyte concentration and the pH value are basically kept unchanged; the deposition time was set to 720 h. The average thickness of the resulting deposition product was 10.8mm, with a growth rate of 24.14% compared to the single layer cathode deposition thickness.
Example 2
Selecting MgCl with the concentration of 0.15mol/L 2 0.03mol/L of CaCl 2 And 0.0069molNaHCO/L 3 The mixed solution is used as an electrolyte solution; the anode material is ruthenium iridium titanium rod with the diameter of 0.3mm, and two ruthenium iridium titanium rods are selected
The 304 stainless steel bar is used as a cathode, the distance between the cathode and the anode is controlled to be 4cm, the distance between the cathodes connected in parallel is controlled to be 0.5cm, and the depth of the electrode immersed in the liquid level is controlled to be 6 cm; the external power supply selects a voltage-stabilizing direct-current power supply, a constant current mode is adopted, and the current is set to be 20 mA; the electrolyte solution is replaced every 24 hours to ensure that the electrolyte concentration and the pH value are basically kept unchanged; the deposition time was set to 120 h. The average thickness of the resulting deposition product was 2.4mm, with a 26.32% increase in thickness compared to a single layer cathode deposition.
Comparative example 3:
compared to example 2, most of them were the same except that the distance between the two cathodes was adjusted to 3.5cm, i.e., 7 times the diameter of the cathode. The average thickness of the resulting deposition product was 1.9 mm.
Photographs of the mineral deposits obtained according to examples 1 and 2 and comparative example 3 are shown in fig. 3 (in which fig. 3a is a photograph of a parallel mesh cathode and fig. 3b is a photograph of the resulting deposit), fig. 4 (in which fig. 4a is a photograph of a parallel rod cathode and fig. 4b is a photograph of the resulting deposit), and fig. 5 (in which fig. 5a is a photograph of a parallel rod cathode and fig. 5b is a photograph of the resulting deposit). Table 1 lists the average thickness of the deposits obtained in parallel with the cathodes of examples 1 and 2 above and compares them with the thickness of the deposits obtained with a single cathode (i.e. comparative examples 1 and 2, respectively, except that a single cathode and anode were used, with the same conditions). Also, the average thickness of the deposit obtained in parallel with the cathodes of example 2 and comparative example 3 above (i.e. unchanged compared with example 2 except for the use of a two-cathode spacing expansion to 7 times the diameter of the cathode) is shown for comparison. For the double-layer mesh cathode, the deposit thickness growth rate is 24.14%; for a rod cathode, the deposit thickness obtained by parallel connection of the cathodes was increased by 26.32% compared with that of a single cathode. For a rod-shaped cathode, a spacing of 0.5cm (i.e., 1 times the cathode spacing) resulted in a 26.32% increase in deposit thickness over a spacing of 3.5cm (i.e., 7 times the cathode spacing). In addition, the two specific embodiments show that the parallel connection of the cathodes has obvious promotion effect on the thickness growth rate of the deposited minerals, and the growth rate reaches about 25%. The growth rate of the deposit can be further regulated and controlled by adjusting the distance between the parallel cathodes. Meanwhile, by comparing the embodiment 2 with the comparative example 3, it can be found that after the distance between the two cathodes is increased to more than 6 times of the diameter of the cathodes, the promoting effect of the parallel connection of the cathodes on the thickness growth rate of the deposited minerals is eliminated.
TABLE 1
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (7)
1. A method for regulating and controlling the deposition rate of electrochemically induced minerals in parallel by cathodes is characterized by comprising the following steps:
(1) constructing an electrode system consisting of cathodes, anodes and electrolyte solution, wherein the number of the cathodes is two, and the anodes are respectively fixed on the outer sides of the two cathodes;
(2) adjusting the distance between the two cathodes to realize the regulation and control of the mineral deposition rate on the surface of the cathode;
the two cathodes are respectively parallel to the anodes positioned at the outer sides of the two cathodes;
the two cathodes are respectively the same as the distance between the anode positioned at the outer side of the two cathodes;
the distance between the two cathodes is within 6 times of the width or diameter of the cathodes;
the electrolyte solution is an aqueous solution containing magnesium ions.
2. The method of claim 1, wherein the smaller the distance between the two cathodes is, the greater the mineral deposition rate on the surface of the cathode is increased.
3. The method for regulating and controlling the deposition rate of the electrochemically induced minerals through the parallel connection of the cathodes as claimed in claim 1, wherein the two cathodes are connected in parallel, and the two cathodes are the same in material and size.
4. The method for regulating and controlling the deposition rate of the electrochemically induced minerals in parallel through the cathodes as claimed in claim 1, wherein the cathodes are metal sheets, metal nets or metal rods.
5. The method for regulating and controlling the deposition rate of the electrochemically induced minerals by the parallel connection of the cathodes as claimed in claim 1, wherein the anodes are ruthenium iridium titanium sheets or platinum sheets.
6. The method as claimed in claim 1, wherein the electrolyte solution is an aqueous solution containing magnesium ions and calcium ions.
7. The method of claim 1, wherein the cathode and the anode are connected to a negative electrode and a positive electrode of an external power source, respectively.
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